CN106972064A - Complex thin film structure photovoltaic device and preparation method - Google Patents
Complex thin film structure photovoltaic device and preparation method Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000004065 semiconductor Substances 0.000 claims abstract description 26
- 239000002346 layers by function Substances 0.000 claims abstract description 21
- 230000005621 ferroelectricity Effects 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims abstract description 14
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 12
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 13
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000033228 biological regulation Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910000859 α-Fe Inorganic materials 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052774 Proactinium Inorganic materials 0.000 claims description 2
- 238000000137 annealing Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 230000003111 delayed effect Effects 0.000 claims 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 16
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 238000001228 spectrum Methods 0.000 abstract description 5
- 230000009466 transformation Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000003595 spectral effect Effects 0.000 abstract 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 6
- 230000012010 growth Effects 0.000 description 6
- 238000005286 illumination Methods 0.000 description 5
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical group O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 5
- 238000004549 pulsed laser deposition Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910017214 AsGa Inorganic materials 0.000 description 3
- 229910002902 BiFeO3 Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IKUCKMMEQAYNPI-UHFFFAOYSA-N [Pb].CN.[I] Chemical class [Pb].CN.[I] IKUCKMMEQAYNPI-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000002128 reflection high energy electron diffraction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- IWXBAFPAYLDYOJ-UHFFFAOYSA-N [Pb].[Zr].[Ti] Chemical group [Pb].[Zr].[Ti] IWXBAFPAYLDYOJ-UHFFFAOYSA-N 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- -1 cushion Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0324—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIVBVI or AIIBIVCVI chalcogenide compounds, e.g. Pb Sn Te
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Complex thin film structure photovoltaic device and preparation method, are related to photoelectric conversion technique and laminated film technical field of solar.The complex thin film structure photovoltaic device of the present invention includes ferroelectricity functional layer, Semiconductor substrate, transparency electrode and bottom electrode, it is characterized in that, cushion is provided between ferroelectric layer and Semiconductor substrate, the material of the cushion is strontium titanates or titanium oxide, and buffer layer thickness is 10~30nm.The present invention has the beneficial effect that：1st, ferroelectric material and semi-conducting material are combined, so as to widen the spectral absorption scope of complex thin film structure photovoltaic device, realize the absorption bands of more spectrum.2nd, by inserting strontium titanates (STO) cushion, the lattice mismatch issue between functional layer and substrate is solved, photo-generated carrier being combined in boundary defect is reduced, significantly improves photoelectric transformation efficiency.
Description
Technical field
The present invention relates to photoelectric conversion technique and laminated film technical field of solar, more particularly to a kind of laminated film
Structure photovoltaic device and preparation method.
Background technology
Methylamine lead iodine class (CH3NH3PbI3) material with perovskite structure is forming thin with contaminating quick Material cladding at present
Film solar cell obtains important breakthrough, and battery efficiency is up to more than 10%.These are broken through for perovskite material and the existing sun
Energy technology of preparing is compound and obtains new and effective solar film battery and sees hope.It is used as the iron for being all perovskite structure
Electroxidation thing has huge photovoltage because of it, also receives much attention always.Particularly in the recent period in new ferroelectric material
Up to 16 volts of photovoltage and strong UV Absorption characteristic are observed on BiFeO3 (BFO), makes perovskite material in cleaning
There are more selections in the application that the energy is obtained.Because both are all perovskite structure, in energy band, valence electron/electrons structure, electricity
Lotus transports and electric charge has many similarities with physical characteristics such as the responses in outfield.Relative to methylamine lead iodine class material, calcium titanium
The crystal structure of ore deposit ferroelectric oxide is more stablized, and is easier to together with the integrated growth of existing semiconductor technology, forms high
Imitate laminated film solar cell.By taking PZT/GaAs extension hetero-junctions as an example, GaAs is a kind of important photovoltaic material in itself, single
The GaAs of knot can absorb visible ray, produce about 0.7 volt of photovoltage.If can be with perovskite ferroelectric materials formation hetero-junctions, two
Person's absorption bands can be complementary, realizes broadband, the conversion of broader spectrum of light energy absorption, obtains the novel thin film with high open circuit voltage
Solar cell.
The present invention illustrates a kind of new laminated film solar battery structure and preparation side exemplified by inserting STO cushions
Method.In order to obtain bigger short circuit current flow, broadband, the light energy absorption conversion of more spectrum are realized, obtaining has high open circuit voltage
Novel compound film solar cell, then obtain that lattice is perfect, high electricity conversion perovskite ferroelectric film seems
It is particularly important.However, in most of reports, after perovskite ferroelectric materials filming, relative to monocrystalline or ceramic material, photoelectricity
Conversion capability is relatively low.The row polycrystalline BTO films that such as prepared by sputtering are it is observed that with the photovoltaic effect of polarization change, but film knot
Structure defect is too many and polarization is less than normal, causes photo-generated carrier to be combined in fault location and can not produce effective photoelectric conversion.Even if
Texture and ferroelectricity well mix lanthanum pzt thin film, because insulating properties is too high, photo-generated carrier can not be formed effectively in thin-film body
Transport, although larger photovoltaic voltage can be produced, but photo-generated carrier is in na magnitude.So only solve perovskite ferroelectric
The problem of photoelectric transformation efficiency declines during filming, could allow the advantage of perovskite ferroelectric photovoltaic property to be played.
For ferroelectric layer/cushion/semiconductor substrate structure photovoltaic device.Generally using nickel (Ni), golden (Au), aluminium
(Al), the grade of silver-colored (Ag) is used as electrode material.Electrode material is also to influence a key factor of film photoelectric transformation efficiency.Its
Include transparency of electrode etc..
The content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the invention provides a kind of ferroelectric layer/cushion/Semiconductor substrate knot
Structure photovoltaic device and preparation method thereof so that the photoelectric transformation efficiency of photovoltaic device is significantly lifted, the especially short circuit of device
Electric current is remarkably enhanced.
The present invention solves the technical scheme that the technical problem uses, complex thin film structure photovoltaic device, including ferroelectricity
Functional layer, Semiconductor substrate, transparency electrode and bottom electrode, it is characterised in that be provided between ferroelectric layer and Semiconductor substrate
Cushion, the material of the cushion is strontium titanates or titanium oxide, and buffer layer thickness is 10~30nm.
Further, the cushioning layer material is strontium titanates, and thickness is 20nm.
The material of the transparency electrode is tin indium oxide or Al-Doped ZnO, and the material of the ferroelectricity functional layer is zirconium titanium
Lead plumbate or bismuth ferrite, the material of Semiconductor substrate is GaAs.
The transparency electrode is face electrode, and the bottom electrode is point electrode.
The present invention also provides a kind of preparation method of complex thin film structure photovoltaic device, it is characterised in that including following steps
Suddenly：
1) cushion of 10~30 nano thickness is deposited on a semiconductor substrate, and the material of cushion is strontium titanates or oxidation
Titanium；
2) ferroelectricity functional layer is grown on the buffer layer；
3) Top electrode is deposited in ferroelectricity functional layer, Top electrode is transparent face electrode；
4) in the bottom surface deposition bottom electrode of Semiconductor substrate, bottom electrode is point electrode.
The present invention has the beneficial effect that：
1st, ferroelectric material and semi-conducting material are combined, so that the spectrum for having widened complex thin film structure photovoltaic device is inhaled
Scope is received, the absorption bands of more spectrum is realized.
2nd, by inserting strontium titanates (STO) cushion, the lattice mismatch issue between functional layer and substrate is solved, is reduced
Photo-generated carrier is compound in boundary defect, significantly improves photoelectric transformation efficiency.
Brief description of the drawings
The structural representation of laminated film photovoltaic device during Fig. 1 arranges for present invention specific implementation.
Fig. 2 show the XRD using the PLD hetero-junctions grown in present invention specific implementation case, and illustration is to wave song
Line.
Fig. 3 show the in-situ monitoring (RHEED) using the LMBE cushion STO grown in present invention specific implementation case
High-energy electron diffiraction figure.
Fig. 4 show the ferroelectric hysteresis loop figure of device in present invention specific implementation case.
Fig. 5 show in the present invention specific implementation case device under the irradiation of standard sunshine, short circuit current flow with
The change curve of voltage.In Fig. 5, three curves are sequentially from up to down：Positive Poling,Un-Poling,
Negative Poling.
Fig. 6 show the short circuit current flow of device in present invention specific implementation case with the change curve of intensity of illumination.
Fig. 7 show the open-circuit voltage of device in present invention specific implementation case with the change curve of intensity of illumination.
Embodiment
The invention discloses a kind of photovoltaic device of ferroelectricity/cushion/semiconductor substrate structure, including Top electrode, lower electricity
Pole, ferroelectricity functional layer and Semiconductor substrate, and the cushion inserted.The present invention solves ferroelectricity function by inserting cushion
Lattice mismatch issue between layer and Semiconductor substrate.
The Top electrode of present embodiment is transparency electrode, and material is conductive film tin indium oxide (ITO).Bottom electrode is aluminium
(Al), silver-colored (Ag) electrode.Ferroelectricity functional layer is lead zirconate titanate (PZT) film, and thickness is 150 nanometers.
It is preferred that, the material of cushion is strontium titanates (STO), and thickness is 20 nanometers.
Semiconductor substrate is GaAs (AsGa) material.
The invention also discloses a kind of preparation method of laminated film photovoltaic device, comprise the steps：
(1) Pulsed laser molecular beam epitaxy (L-MBE) technology is utilized, 20 nano thickness STO are deposited on a semiconductor substrate
Cushion.
(2) using pulsed laser deposition technique (PLD), the ferroelectricity functional layer of 150 nano thickness is grown on the buffer layer.
(3) pulsed laser deposition Top electrode is utilized in ferroelectricity functional layer, Top electrode is face electrode.
(4) bottom electrode is deposited using electron beam evaporation technique on a semiconductor substrate, bottom electrode is point electrode.
Further, in described step (1), STO buffer growths use L-MBE technologies on AsGa substrates.
The present invention carries out in-situ monitoring using high electron energy diffractometer (RHEED).
The ferroelectricity functional layer material is Pb (Zr(1-x),Tix)O3, using PbO, La2O3、TiO2Matched for raw material,
Wherein, x=0.48.
Further, the step (2) specifically includes：
PZT targets are utilized respectively absolute ethyl alcohol and deionized water is cleaned by ultrasonic 5 minutes, arteries and veins is put into after high pressure nitrogen drying
Laser splash vacuum cavity is rushed, substrate is heated to 550 DEG C, is evacuated to 1 × 10-1Below Pa, then open flowmeter with
50sccm flow is passed through oxygen to cavity, and regulation cavity to 20Pa after after cavity stable gas pressure, opens laser, adjusts and swash
Light frequency is 3Hz, and laser energy is 5J/cm-2, sputter 30 minutes, close lasing light emitter, regulation flow value 200sccm flow is treated
Cavity stable gas pressure is 1 × 103Pa, in-situ annealing 30 minutes, opens cavity, sample is taken out afterwards.
Prepare Top electrode and use PLD systems, prepare bottom electrode and use electron-beam vapor deposition method.
Embodiment
The embodiment of the invention discloses a kind of complex thin film structure photovoltaic device, including transparency electrode (Top electrode), ferroelectricity
Functional layer, cushion, Semiconductor substrate and lower metal electrode.
The preferred strontium titanates of cushion (STO) or titanium oxide (TiO2)；Transparent conductive electrode be preferably tin indium oxide (ITO) or
The transparent conductive materials such as person's Al-Doped ZnO；Lower metal electrode is aluminium (Al) or silver-colored (Ag)；Ferroelectricity functional layer is lead zirconate titanate
Or bismuth ferrite (BFO) (PZT)；Semiconductor substrate is preferably GaAs (AsGa).
The present embodiment provides pair of two kinds of devices of ITO/PZT/STO/GaAs/Al structures and ITO/PZT/GaAs/Al structures
Than.ITO is transparent conductive electrode, will not weaken the absorption of functional layer and substrate to light.The preferred strontium titanates of cushion (STO),
STO lattice constant is 0.392 nanometer.Functional layer is preferably PZT, and PZT lattice constant is 0.402 nanometer.Semiconductor is served as a contrast
Bottom is preferably GaAs, and GaAs lattice constant is 0.565 nanometer, test result indicates that cushion is rotation 45 degree with substrate
With growth.Cushion and function growth structure are good.Because crystalline structure growth is good, the short circuit current flow and open circuit of device
Voltage is obviously improved.Especially short circuit current flow improves about 10000 times.
Below in conjunction with the accompanying drawing in present example, the technical scheme in present example is described in detail.
As shown in figure 1, the present invention complex thin film structure photovoltaic device include electrically conducting transparent Top electrode, PZT functional layers,
STO cushions, GaAs substrates and lower metal electrode.Device is 5 × 5cm2Size, transparent conductive electrode thickness be 100nm,
Bottom electrode is metal point electrode.
Fig. 2 for the present invention complex thin film structure photovoltaic device XRD, and as a comparison do not possess cushion show
There is the XRD of technology.Illustration is rocking curve.
It is special in growth course that in-situ monitoring, diffraction pattern are carried out using high electron energy diffractometer because buffer layer thickness is too thin
As shown in Figure 3.
Sample is subjected to test ferroelectric hysteresis loop, such as Fig. 4.
Sample is placed in below a simulated solar irradiation and obtains the I-V curve of device for shown in Fig. 5.
Adjust the varying strength of illumination respectively, measure the current density of device changed with the difference of intensity of illumination as
Shown in Fig. 6, the open-circuit voltage of device changes as shown in Figure 7 with the difference of intensity of illumination.
Claims (6)
1. complex thin film structure photovoltaic device, including ferroelectricity functional layer, Semiconductor substrate, transparency electrode and bottom electrode, its feature
It is, cushion is provided between ferroelectric layer and Semiconductor substrate, the material of the cushion is strontium titanates or titanium oxide, is delayed
Thickness degree is rushed for 10~30nm.
2. complex thin film structure photovoltaic device as claimed in claim 1, it is characterised in that the cushioning layer material is metatitanic acid
Strontium, thickness is 20nm.
3. complex thin film structure photovoltaic device as claimed in claim 1, it is characterised in that the material of the transparency electrode is oxygen
Change indium tin or Al-Doped ZnO, the material of the ferroelectricity functional layer is lead zirconate titanate or bismuth ferrite, the material of Semiconductor substrate
Expect for GaAs.
4. the complex thin film structure photovoltaic device as described in right wants 3, it is characterised in that the transparency electrode is face electrode, institute
Bottom electrode is stated for point electrode.
5. the preparation method of complex thin film structure photovoltaic device, it is characterised in that comprise the steps：
1) cushion of 10~30 nano thickness is deposited on a semiconductor substrate, and the material of cushion is strontium titanates or titanium oxide；
2) ferroelectricity functional layer is grown on the buffer layer；
3) Top electrode is deposited in ferroelectricity functional layer, Top electrode is transparent face electrode；
4) in the bottom surface deposition bottom electrode of Semiconductor substrate, bottom electrode is point electrode.
6. the preparation method of complex thin film structure photovoltaic device, it is characterised in that the step 2) be：
PZT targets are utilized respectively absolute ethyl alcohol and deionized water is cleaned by ultrasonic 5 minutes, being put into pulse after high pressure nitrogen drying swashs
Light sputters vacuum cavity, and substrate is heated to 550 DEG C, is evacuated to 1 × 10-1Below Pa, then with 50sccm flow to cavity
Oxygen is passed through, cavity is adjusted to 20Pa, after after cavity stable gas pressure, opening laser, regulation laser frequency is 3Hz, laser energy
Measure as 5J/cm-2, sputter 30 minutes, close lasing light emitter, regulation flow value 200sccm flow, treat cavity stable gas pressure 1 ×
103Pa, in-situ annealing 30 minutes.
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